The catalytic performance of two oxides coated anodes （OCSs） meshes and one OCA plate was investigated in a zinc electrowinning electrolyte at 38 ℃. Their electrochemical behaviors were compared with that of a conv...The catalytic performance of two oxides coated anodes （OCSs） meshes and one OCA plate was investigated in a zinc electrowinning electrolyte at 38 ℃. Their electrochemical behaviors were compared with that of a conventional Pb-0.7%Ag alloy anode. Electrochemical measurements such as cyclic voltammetric, galvanostatic, potentiodynamic, open-circuit potential （OCP） and in situ electrochemical noise measurements were considered. After 2 h of OCP test, the linear polarization shows that the corrosion current density of the Ti/（IrO2-Ta2O5） mesh electrode is the lowest （3.37μA/cm^2） among the three OCAs and shows excellent performance. Additionally, after 24 h of galvanostatic polarization at 50 mA/cm^2and 38 ℃, the Ti/MnO2mesh anode has the highest potential （1.799 V）, followed by the Ti/（IrO2-Ta2O5） plate （1.775 V） and Ti/（IrO2-Ta2O5） mesh （1.705 V） anodes. After 24 h of galvanostatic polarization followed by 16 h of decay, the linear polarization method confirms the sequence obtained after 2 h of OCP test, and the Ti/（IrO2-Ta2O5） mesh attains the lowest corrosion current density. The Ti/（IrO2-Ta2O5） mesh anode also shows better performance after 24 h of galvanostatic polarization with the overpotential lower than that of the conventional Pb-Ag anode by about 245 mV.展开更多
Quantum chemical calculations are performed to study the reactions of OH and ozone with- out and with water to estimate whether the single water molecule can decrease the energy barrier of the OH radical reaction with...Quantum chemical calculations are performed to study the reactions of OH and ozone with- out and with water to estimate whether the single water molecule can decrease the energy barrier of the OH radical reaction with ozone. The calculated results demonstrate that the single water molecule can reduce the activated barrier of the naked OH＋Oa reaction with the value of about 4.18 kJ/mol. In addition, the transition state theory is carried out to determine whether the single water molecule could enhance the rate constant of the OH＋O3 reaction. The computed kinetic data indicate that the rate of the ozone reaction with the formed complexes between OH and water is much slower than that of the OH＋O3 reaction, whereas the rate constant of OH reaction with the formed H20---Oa complex is 2 times greater than that of the naked OH radical with ozone reaction. However, these processes in the atmosphere are not important because the reactions can not compete well with the naked reaction of OH with ozone under atmospheric condition.展开更多
Rock weathering plays an important role in studying the long-term carbon cycles and global climatic change. According to the statistics analysis, the Huanghe (Yellow) River water chemistry was mainly controlled by eva...Rock weathering plays an important role in studying the long-term carbon cycles and global climatic change. According to the statistics analysis, the Huanghe (Yellow) River water chemistry was mainly controlled by evaporite and carbonate weathering, which were responsible for over 90% of total dissolved ions. As compared with the Huanghe River basin, dissolved load of the Changjiang (Yangtze) River was mainly originated from the carbonate dissolution. The chemical weathering rates were estimated to be 39.29t/(km(2).a) and 61.58t/(km(2).a) by deducting the HCO3- derived from atmosphere in the Huanghe River and Changjiang River watersheds, respectively. The CO2 consumption rates by rock weathering were calculated to be 120.84 x 10(3)mol/km(2) and 452.46 x 10(3)mol/km(2) annually in the two basins, respectively. The total CO2 consumption of the two basins amounted to 918.51 x 10(9)mol/a, accounting for 3.83% of the world gross. In contrast to other world watersheds, the stronger evaporite reaction and infirm silicate weathering can explain such feature that CO2 consumption rates were lower than a global average, suggesting that the sequential weathering may be go on in the two Chinese drainage basins.展开更多
Freeze drying has a deleterious effect on the viability of microorganisms. In front of this difficulty, the present study adopts response surface methodology to optimize the chemical compositions of protective agents ...Freeze drying has a deleterious effect on the viability of microorganisms. In front of this difficulty, the present study adopts response surface methodology to optimize the chemical compositions of protective agents to seek for maximum viability of Bifidobacterium longum BIOMA 5920 during freeze-drying. Through the compara- tive analysis of single protectant, the complex protective agents show better effect on the Bifidobacterium viability. Human-like collagen (HLC), trehalose and glycerol are confirmed as significant factors by Box-Behnken Design. The optimized formula for these three variables is tested as follows: HLC 1.23%, trehalose 11.50% and glycerol 4.65%. Under this formula, the viability is 88.23%, 39.67% higher in comparison to the control. The viable count is 1.07×10 9 cfu·g-1 , greatly exceeding the minimum viable count requirement (10 6 cfu·g-1 ).展开更多
Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have be...Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have been rarely reported.Herein,a CoP co-catalyst-modified graphitic-C3N4(g-C3N4/CoP)is investigated for photocatalytic water splitting to produce H2.The g-C3N4/CoP composite is synthesized in two steps.The first step is related to thermal decomposition,and the second step involves an electroless plating technique.The photocatalytic activity for hydrogen evolution reactions of g-C3N4 is distinctly increased by loading the appropriate amount of CoP quantum dots(QDs).Among the as-synthesized samples,the optimized one(g-C3N4/CoP-4%)shows exceptional photocatalytic activity as compared with pristine g-C3N4,generating H2 at a rate of 936μmol g^-1 h^-1,even higher than that of g-C3N4 with 4 wt%Pt(665μmol g^-1 h^-1).The UV-visible and optical absorption behavior confirms that g-C3N4 has an absorption edge at 451 nm,but after being composited with CoP,g-C3N4/CoP-4%has an absorption edge at 497 nm.Furthermore,photoluminescence and photocurrent measurements confirm that loading CoP QDs to pristine g-C3N4 not only enhances the charge separation,but also improves the transfer of photogenerated e--h+pairs,thus improving the photocatalytic performance of the catalyst to generate H2.This work demonstrates a feasible strategy for the synthesis of highly efficient metal phosphide-loaded g-C3N4 for hydrogen generation.展开更多
The effects of trace element Fe on the corrosion behavior of AZ80 magnesium alloy were investigated by salt spray test and electrochemical measurements.The results show that the corrosion rate decreases with decreasin...The effects of trace element Fe on the corrosion behavior of AZ80 magnesium alloy were investigated by salt spray test and electrochemical measurements.The results show that the corrosion rate decreases with decreasing the trace element Fe content in an approximately linear relation even though the amount of trace element Fe reduces to 0.000 2%(mass fraction).The electrochemical measurements show that the corrosion potential(φcorr)of the alloy with lower trace element Fe content shifts to less negative value.It is suggested that the control trace element by purification is an effective way to enhance the corrosion resistance of AZ80 magnesium alloy.展开更多
Electrochemical measurement, quantum chemical method, and scanning electron microscopy （SEM） were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride （TTC） and 2,4,6-tri（2-py...Electrochemical measurement, quantum chemical method, and scanning electron microscopy （SEM） were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride （TTC） and 2,4,6-tri（2-pyridyl） -s-triazine（TPT） on the corrosion of mild steel in lmol.L^-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mecha-nism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal-was protected from aggressive corrosion by the addition of TTC and TPT.展开更多
Among all the DNA components, extremely redox-active guanine （G） and adenine （A） bases are subject to facile loss of an electron and form cation radicals （G＋＂ and A＋＇） when exposed to irradiation or radical ...Among all the DNA components, extremely redox-active guanine （G） and adenine （A） bases are subject to facile loss of an electron and form cation radicals （G＋＂ and A＋＇） when exposed to irradiation or radical oxidants. The subsequent deprotonation of G＋＇ and A＋＇ can invoke DNA damage or interrupt hole transfer in DNA. However, compared with intensive reports for G＋, studies on the deprotonation of A＋ are still limited at present. Herein, we investigate the deprotonation behavior of A＋. by time-resolved laser flash photolysis. The deprotonation product of A（N6-H）＇ is observed and the deprotonation rate constant, （2.0±0.1）×10 7 s-1, is obtained at room temperature. Further, the deprotonation rate con- stants of A＋. are measured at temperatures varying from 280 K to 300 K, from which the activation energy for the N6-H deprotonation is determined to be （17.1±1.0） kJ/mol by Arrhenius equation. In addition, by incorporating the aqueous solvent effect, we perform density functional theory calculations for A＋ deprotonation in free base and in duplex DNA. Together with experimental results, the deprotonation mechanisms of A＋ in free base and in duplex DNA are revealed, which are of fundamental importance for understanding the oxidative DNA damage and designing DNA-based electrochemical devices.展开更多
Mg-6%Al-5%Pb and Mg-6%Al-5%Pb-0.55%Zn-0.22%Mn(mass fraction) alloys were prepared by induction melting with the protection of argon.The corrosion behaviors of these alloys were studied by electrochemical measurements ...Mg-6%Al-5%Pb and Mg-6%Al-5%Pb-0.55%Zn-0.22%Mn(mass fraction) alloys were prepared by induction melting with the protection of argon.The corrosion behaviors of these alloys were studied by electrochemical measurements and immersion tests.The results show that at the corrosion onset of Mg-Al-Pb anode there is an incubation period that can be shortened with 0.55%Zn and 0.22%Mn additions in the magnesium matrix.The corrosion rate of Mg-Al-Pb anode is mainly determined by the incubation period.Short incubation period always leads to high corrosion rate while long incubation period leads to low corrosion rate.The corrosion rates based on the corrosion current density by the electrochemical measurements do not agree with the measurements evaluated from the evolved hydrogen volume.展开更多
基金Project(RDCPJ 428402)supported by the Natural Sciences and Engineering Research Council of Canada
文摘The catalytic performance of two oxides coated anodes （OCSs） meshes and one OCA plate was investigated in a zinc electrowinning electrolyte at 38 ℃. Their electrochemical behaviors were compared with that of a conventional Pb-0.7%Ag alloy anode. Electrochemical measurements such as cyclic voltammetric, galvanostatic, potentiodynamic, open-circuit potential （OCP） and in situ electrochemical noise measurements were considered. After 2 h of OCP test, the linear polarization shows that the corrosion current density of the Ti/（IrO2-Ta2O5） mesh electrode is the lowest （3.37μA/cm^2） among the three OCAs and shows excellent performance. Additionally, after 24 h of galvanostatic polarization at 50 mA/cm^2and 38 ℃, the Ti/MnO2mesh anode has the highest potential （1.799 V）, followed by the Ti/（IrO2-Ta2O5） plate （1.775 V） and Ti/（IrO2-Ta2O5） mesh （1.705 V） anodes. After 24 h of galvanostatic polarization followed by 16 h of decay, the linear polarization method confirms the sequence obtained after 2 h of OCP test, and the Ti/（IrO2-Ta2O5） mesh attains the lowest corrosion current density. The Ti/（IrO2-Ta2O5） mesh anode also shows better performance after 24 h of galvanostatic polarization with the overpotential lower than that of the conventional Pb-Ag anode by about 245 mV.
基金This work was supported by the National Natural Science Foundation of China （No.10865003） and the Science and Technology Foundation of GuiZhou Province, China （No.[201112107）. We thank the Key Laboratory of Guizhou High Performance Computational Chemistry for computer time.
文摘Quantum chemical calculations are performed to study the reactions of OH and ozone with- out and with water to estimate whether the single water molecule can decrease the energy barrier of the OH radical reaction with ozone. The calculated results demonstrate that the single water molecule can reduce the activated barrier of the naked OH＋Oa reaction with the value of about 4.18 kJ/mol. In addition, the transition state theory is carried out to determine whether the single water molecule could enhance the rate constant of the OH＋O3 reaction. The computed kinetic data indicate that the rate of the ozone reaction with the formed complexes between OH and water is much slower than that of the OH＋O3 reaction, whereas the rate constant of OH reaction with the formed H20---Oa complex is 2 times greater than that of the naked OH radical with ozone reaction. However, these processes in the atmosphere are not important because the reactions can not compete well with the naked reaction of OH with ozone under atmospheric condition.
基金Undertheauspicesof Ministry of Science and Technology Project of China (No. G1999043075)
文摘Rock weathering plays an important role in studying the long-term carbon cycles and global climatic change. According to the statistics analysis, the Huanghe (Yellow) River water chemistry was mainly controlled by evaporite and carbonate weathering, which were responsible for over 90% of total dissolved ions. As compared with the Huanghe River basin, dissolved load of the Changjiang (Yangtze) River was mainly originated from the carbonate dissolution. The chemical weathering rates were estimated to be 39.29t/(km(2).a) and 61.58t/(km(2).a) by deducting the HCO3- derived from atmosphere in the Huanghe River and Changjiang River watersheds, respectively. The CO2 consumption rates by rock weathering were calculated to be 120.84 x 10(3)mol/km(2) and 452.46 x 10(3)mol/km(2) annually in the two basins, respectively. The total CO2 consumption of the two basins amounted to 918.51 x 10(9)mol/a, accounting for 3.83% of the world gross. In contrast to other world watersheds, the stronger evaporite reaction and infirm silicate weathering can explain such feature that CO2 consumption rates were lower than a global average, suggesting that the sequential weathering may be go on in the two Chinese drainage basins.
基金Supported by the National High Technology Research and Development Program of China (2007AA03Z456)the National Natural Science Foundation of China (20776119, 21076169 and 31000019)+5 种基金the Xi’an Research and Development Program(NC08005, YF07078)the Scientific Research Program of Shaanxi Provincial Department of Education,China(08JK452,08JK453,JG08181,2010JC21,2010JS107,2010JS108, 2010JK876 and 2010JS109)Shaanxi Provincial Scientific Technology Research and Development Program (2007K06-03, 2010JQ2012, SJ08B03)the Specialized Research Fund for the Doctoral Program of Higher Education of China (20096101120023, 20096101110014)NWU Graduate Innovation and Creativity Funds (08YSY17)Shaanxi Key Subject Program, China
文摘Freeze drying has a deleterious effect on the viability of microorganisms. In front of this difficulty, the present study adopts response surface methodology to optimize the chemical compositions of protective agents to seek for maximum viability of Bifidobacterium longum BIOMA 5920 during freeze-drying. Through the compara- tive analysis of single protectant, the complex protective agents show better effect on the Bifidobacterium viability. Human-like collagen (HLC), trehalose and glycerol are confirmed as significant factors by Box-Behnken Design. The optimized formula for these three variables is tested as follows: HLC 1.23%, trehalose 11.50% and glycerol 4.65%. Under this formula, the viability is 88.23%, 39.67% higher in comparison to the control. The viable count is 1.07×10 9 cfu·g-1 , greatly exceeding the minimum viable count requirement (10 6 cfu·g-1 ).
基金supported by the National Natural Science Foundation of China(51602207)the Doctoral Scientific Research Foundation of Liaoning Province(20170520011)+3 种基金the Program for Liaoning Excellent Talents in Universities(LR2017074)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE-201810)Fuzhou University,the Scientific Research Project of the Educational Department of Liaoning Province(LQN201712)Shenyang Excellent Talents in Universities(RC180211)~~
文摘Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have been rarely reported.Herein,a CoP co-catalyst-modified graphitic-C3N4(g-C3N4/CoP)is investigated for photocatalytic water splitting to produce H2.The g-C3N4/CoP composite is synthesized in two steps.The first step is related to thermal decomposition,and the second step involves an electroless plating technique.The photocatalytic activity for hydrogen evolution reactions of g-C3N4 is distinctly increased by loading the appropriate amount of CoP quantum dots(QDs).Among the as-synthesized samples,the optimized one(g-C3N4/CoP-4%)shows exceptional photocatalytic activity as compared with pristine g-C3N4,generating H2 at a rate of 936μmol g^-1 h^-1,even higher than that of g-C3N4 with 4 wt%Pt(665μmol g^-1 h^-1).The UV-visible and optical absorption behavior confirms that g-C3N4 has an absorption edge at 451 nm,but after being composited with CoP,g-C3N4/CoP-4%has an absorption edge at 497 nm.Furthermore,photoluminescence and photocurrent measurements confirm that loading CoP QDs to pristine g-C3N4 not only enhances the charge separation,but also improves the transfer of photogenerated e--h+pairs,thus improving the photocatalytic performance of the catalyst to generate H2.This work demonstrates a feasible strategy for the synthesis of highly efficient metal phosphide-loaded g-C3N4 for hydrogen generation.
基金Project(2007CB613705)supported by the National Basic Research Program of China
文摘The effects of trace element Fe on the corrosion behavior of AZ80 magnesium alloy were investigated by salt spray test and electrochemical measurements.The results show that the corrosion rate decreases with decreasing the trace element Fe content in an approximately linear relation even though the amount of trace element Fe reduces to 0.000 2%(mass fraction).The electrochemical measurements show that the corrosion potential(φcorr)of the alloy with lower trace element Fe content shifts to less negative value.It is suggested that the control trace element by purification is an effective way to enhance the corrosion resistance of AZ80 magnesium alloy.
基金Supported by Key Projects of National Knowledge Innovation Program at Chinese Academy of Sciences (Kzcx2-yw-210-03).
文摘Electrochemical measurement, quantum chemical method, and scanning electron microscopy （SEM） were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride （TTC） and 2,4,6-tri（2-pyridyl） -s-triazine（TPT） on the corrosion of mild steel in lmol.L^-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mecha-nism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal-was protected from aggressive corrosion by the addition of TTC and TPT.
文摘Among all the DNA components, extremely redox-active guanine （G） and adenine （A） bases are subject to facile loss of an electron and form cation radicals （G＋＂ and A＋＇） when exposed to irradiation or radical oxidants. The subsequent deprotonation of G＋＇ and A＋＇ can invoke DNA damage or interrupt hole transfer in DNA. However, compared with intensive reports for G＋, studies on the deprotonation of A＋ are still limited at present. Herein, we investigate the deprotonation behavior of A＋. by time-resolved laser flash photolysis. The deprotonation product of A（N6-H）＇ is observed and the deprotonation rate constant, （2.0±0.1）×10 7 s-1, is obtained at room temperature. Further, the deprotonation rate con- stants of A＋. are measured at temperatures varying from 280 K to 300 K, from which the activation energy for the N6-H deprotonation is determined to be （17.1±1.0） kJ/mol by Arrhenius equation. In addition, by incorporating the aqueous solvent effect, we perform density functional theory calculations for A＋ deprotonation in free base and in duplex DNA. Together with experimental results, the deprotonation mechanisms of A＋ in free base and in duplex DNA are revealed, which are of fundamental importance for understanding the oxidative DNA damage and designing DNA-based electrochemical devices.
基金Project(JPPT-115-168) supported by National Key Science and Technological Project of China
文摘Mg-6%Al-5%Pb and Mg-6%Al-5%Pb-0.55%Zn-0.22%Mn(mass fraction) alloys were prepared by induction melting with the protection of argon.The corrosion behaviors of these alloys were studied by electrochemical measurements and immersion tests.The results show that at the corrosion onset of Mg-Al-Pb anode there is an incubation period that can be shortened with 0.55%Zn and 0.22%Mn additions in the magnesium matrix.The corrosion rate of Mg-Al-Pb anode is mainly determined by the incubation period.Short incubation period always leads to high corrosion rate while long incubation period leads to low corrosion rate.The corrosion rates based on the corrosion current density by the electrochemical measurements do not agree with the measurements evaluated from the evolved hydrogen volume.
